CN103781830B - High performance lagging material - Google Patents
High performance lagging material Download PDFInfo
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- CN103781830B CN103781830B CN201280044527.3A CN201280044527A CN103781830B CN 103781830 B CN103781830 B CN 103781830B CN 201280044527 A CN201280044527 A CN 201280044527A CN 103781830 B CN103781830 B CN 103781830B
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-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/06—Constructions of heat-exchange apparatus characterised by the selection of particular materials of plastics material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0064—Multimodal pore size distribution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/042—Nanopores, i.e. the average diameter being smaller than 0,1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/048—Bimodal pore distribution, e.g. micropores and nanopores coexisting in the same foam
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Silicon Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Civil Engineering (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Thermal Insulation (AREA)
- Environmental & Geological Engineering (AREA)
- Building Environments (AREA)
Abstract
The present invention relates to lagging material, be the solid foam form based on the silica dioxide granule with sub-micron pore porosity especially, described material has two different porosity ranges, advantageously comprise the first scope be made up of (greatly) hole of the diameter with 10 microns to 3 millimeters, with by having higher than 4nm and the second scope formed lower than the sub-micron porosity of the diameter of 300nm, the volume of voids of described sub-micron porosity is at least 1cm
3the density of/g and described insulating material is lower than 300kg/m
3, and relate to its preparation method.
Description
The present invention relates to high performance lagging material, its preparation method, with it in building field for the wall (outer wall or inwall) of isolated buildings or for being filled in material (hollow wall or " hollow wall ", pipeline, etc.) in the purposes in gap, this insulating material can be the form of panel, or is optionally particle, stick, multilayer, ejecta, the form of mouldings etc.
No matter whether it relates to newly built construction or repairs market, and to effective obstruct product, the demand of insulation product is always king-sized especially.Except the isolated character that improves and the specification of load meeting construction work, also constantly increase providing that larger raw-material use is comfortable, the life-span, saving etc. (especially in order to Sustainable development) the needs of product.This to providing in the exploration of better lagging material, particularly advantageously, described material should also have, and even improves, other character of wishing in bulding, especially in load reduction, physical strength, sound insulation etc.
Multiple lagging material is current is known.In modal product, the fiber insulation based on natural or synthon (as glass wool or asbestos) can be mentioned, the vesicular insulation of expanded polymer type, as expanded or extruded polystyrene, or phenol formaldehyde foam or polyurethane foam.The thermal characteristics of substantially inorganic insulating material is presented as usually above 35, the thermal conductivity value λ of about 40mW/m.K especially, this value when substantially organically insulation, can be such as lower when mixing the vesicular insulation of the gas (to improve thermal characteristics) with the thermal conductivity lower than air.But, a shortcoming of these materials be along with time chien shih this gas remain on intramatrical difficulty, this is because this material loses these thermal characteristicss of a part due to aging.And, for organic insulation, because their character combustion reactions is poor.
The material wherein having produced vacuum (forming such as vacuum panels) can also be used.These insulations are difficult to use, and this also cannot be punctured because they both cannot be cut, and they can experience vacuum leak progressively within long-time period.
The insulation that can also mention is aerogel; it is usually in having the usual particle of millimeter grade or the translucent particle of size of particles or powder type; these aerogels are effective especially in heat insulation; but the mechanical properties of their difference requires that they use together with fender or toughener; or the aerogel in the felt formed by winding fiber (mechanically firm) (or pad); for them, can be difficult to produce the shape determined.These aerogels (especially silicon-dioxide) are difficult at industrial scale obtain and are expensive, and their require that the combination (to obtain physical strength or suitable form) of complicated drying conditions and they and other insulation may be complicated.Therefore their purposes remains restricted.
Therefore to exist exploitation be effective in heat insulation but especially than the strong needs that aerogel is easier and cheaper material in industry preparation.Except its excellent thermal characteristics (improving relative to current inorganic product), desirably, this product has excellent stability (especially ageing resistance, or in physical strength etc.: chemical resistant properties, resistivity against fire etc.) and does not increase its load burden.It is also desirable that it remains and is easy to launch and its allows any desirable shape of preparation between its hardening period, particularly by molded (or optionally by the expansion of layer or injection).
Therefore the present invention develops and allows to realize this object and novel insulating material for overcoming previously mentioned shortcoming; this type material is substantially inorganic, directly (does not need the chemical reaction of chemical constitution by means of changing them) by having an inorganic particle acquisition of two different aperture degree scopes for (having) sub-micron pore porosity (namely comprising the hole had lower than 1 micron diameter).In these materials, the present invention pays close attention to those that obtain from silica dioxide granule especially, this silica dioxide granule has highly porous (higher than such as other inorganic particle, porosity as carbonate or silicate granules) advantage, but this material is more difficult to obtain (such as, than when using previously mentioned carbonate or silicate granules), this is especially due to the small size (being usually less than hundreds of nanometer) of silicon-dioxide, their usual more wetting ability and the difficulty making the porous material of silica dioxide granule and acquisition (foam) stable.The present invention seeks especially to be more suitable for the described production method based on the situation of the material of silica dioxide granule especially, to allow to obtain the thermal properties improved further, and the better stability of the material of the described acquisition of permission in addition.
The present invention is by proposing novel heat insulation material, (at least) is in solid foam form especially, realize this object, this material forms (or be made up of them or based on them) by the silica dioxide granule with sub-micron pore porosity, this material comprises (or comprise or combine) two different (or to distinguish or separate) porosity ranges, advantageously comprise by having 10 microns to 3 millimeters, the first scope (being called as macroporsity in the present invention) of forming of some tens of pm to the hole (being called macropore) of diameter (namely there is diameter Distribution) of hundreds of micron (especially 10 to 500 microns) especially, with by higher than 4nm, preferably higher than 5nm, and lower than 300nm, especially lower than the second scope (being called as sub-micron pore porosity in the present invention) that the hole (being called sub-micron porosity) of the diameter (namely having diameter Distribution) of 200nm (even lower than 100nm) forms, the volume of voids of described sub-micron porosity is at least 1cm
3/ g (i.e. 1cm
3/ gram material) and the density (massevolumique) (apparent or global density, namely measures Total Product) of insulating material for lower than 300kg/m
3.
This material can be obtained by the method comprising following steps:
-at least one preparation has higher than 5m
2/ g, especially higher than 50m
2the specific surface area S of/g, and in 4nm to 300nm porosity ranges, there is at least 1cm
3the step of the mixture (or aggregate) of the silica dioxide granule of the volume of voids of/g, (dispersion, the suspension especially in water) that this mixture is normally moisture;
-at least one prepares the step of foam (moisture (or moistening)), and this foam comprises described particle (use above-mentioned granular mixture and/or by being mixed by described granular mixture in the resistance aqueous foam that formed respectively);
-at least one forming step (usually to form material all in one piece and/or layer), particularly by being molded or casting or spray (on surface or wall) these foams;
The foam of-at least one at least part of dry so acquisition or the step of material (by drying or passing through drying).
This preparation comprising the foam of particle/granular mixture can be carried out:
-by directly spuming: namely by different methods, gas is introduced in granular mixture; as: mechanical stirring, gas sparging; such as through sinter (porous plate; gas is made to pass it to produce foam); dissolved gases (such as pentane) or pass through chemical reaction; particularly by the original position bubbling of the gas that decomposition (such as peroxide decomposition is water and molecular oxygen) produces etc., and/or
-by mixing: namely; granular mixture is mixed (or on the contrary in preformed resistance aqueous foam; preformed foam is mixed in granular mixture); described foam is such as by using spuming and being prepared of dispersion (usually moisture); gas is introduced via one of aforesaid method in this dispersion
Spume and even usually (be added in granular mixture in direct situation foamy at least one tensio-active agent; or when mixing; tensio-active agent is present in dispersion, makes this dispersion spume to form resistance aqueous foam) carry out when existing.
Even if use anionic type tensio-active agent (or salt of aniorfic surfactant) (or surface reagent) to be possible, the present invention is verified, in order to obtain material according to the invention, use the zwitter-ion of one or more betaine-types, advantageously cocamidopropyl betaine (or CAPB, based on lauroyl amido CAB or { [3-(dodecanoylamino) propyl group] (dimethyl) ammonium } acetate) as the advantage of tensio-active agent (one or more), and develop the favourable and effective especially ad hoc approach for being obtained the insulating material improved further by silicon-dioxide (particle) concurrently, this method comprises the following steps:
-at least one preparation has higher than 5m
2/ g, especially higher than 50m
2the specific surface area S of/g, and in 4-300nm porosity ranges, there is at least 1cm
3the step of the mixture (or aggregate) of the silica dioxide granule of the volume of voids of/g, (dispersion, the suspension especially in water) that this mixture is normally moisture;
-at least one to prepare the step of foam from described granular mixture by mixing at least one zwitter-ion (as tensio-active agent), and this zwitter-ion is selected from trimethyl-glycine, especially ammonium trimethyl-glycine, particularly preferred cocamidopropyl betaine;
-at least one forming step (usually to form material all in one piece and/or layer), particularly by being molded or casting or spray (on surface or wall) this foam;
The foam of-at least one at least part of dry so acquisition or the step of material (by drying or passing through drying),
-if desired (in the process preferably), at least one hydrophobization step (the usual hydrophobization of the material of acquisition, but hydrophobization all right/or in another moment, such as carry out with spuming simultaneously).
This method allows to obtain the stable material (silicon dioxide foam) with superior strength and excellent thermal insulation character, as explained hereinafter and illustrational.Especially the ionic interaction (being made the interface stability of particle and foam by described tensio-active agent) observed between above-mentioned amphoteric ionic surfactant and silicon-dioxide allow to be formed excellently foam and excellent particle and moistening foam stability (especially in the face of draining, Ostwald slaking, coalescent etc. time), the stability of this moistening foam is important because its allow preserve between its dry epoch vesicular structure and therefore obtain in gather/solid silica foam.The bubble size that this preferred method also allows to control this foam and the ratio of air of mixing, also allow to obtain and alleviate/controlled the silicon dioxide foam of density.
As according to the present invention define, the product of exploitation comprise two kinds of porosity/two type holes (its significantly difference be their size (observing the different aperture distribution of sizes around two different peaks in the present case), undertaken qualitative by their diameter in the present case), the hole (as sub-micron porosity) of a kind exists between another kind of class hole (as macropore).Usually and advantageously, only two kinds of porosity/type holes are present in this product, but do not get rid of, this product can comprise and be greater than two kinds of porositys/type hole (especially around different distribution of peaks).As explained hereinafter, allow the diameter of qualitative sub-micron porosity to be calculated by the pore volume measurements value by using the mercury of Mona Washbourne (Washburn) equation to invade porosimetry, the diameter of macropore is by scanning electron microscopy (MEB) or measured by x-ray tomography method.
Especially and advantageously, this product has diameter higher than 4nm, especially higher than 5nm, usually above 7nm, especially higher than 10nm and lower than 300nm, be usually less than 200nm especially, even lower than 100nm submicron (according to use primary particles, such as according to their specific surface area, diameter changes within the scope of these, and diameter Distribution can also be more or less narrow or compression around peak) hole (and being formed by the particle with hole).As previously pointed out, this macropore had 10 microns to 3mm, advantageously higher than 50 microns even higher than 100 microns, and advantageously lower than 500 microns even lower than the diameter (namely there is diameter Distribution) of 300 microns.
Preferably, the volume of voids of this sub-micron porosity is 1-3cm
3/ g is especially 1-1.5cm
3/ g, the volume of voids of macropore is higher than 1cm
3/ g (i.e. 1cm
3/ gram material), preferably higher than 3cm
3/ g is 5-15cm especially
3/ g.Volume of voids (the V of this sub-micron porosity
sm) measured by the mercury porosity method of carrying out on the machine of trade mark Pascal140 and Pascal440 by ThermoScientific Company, and be considered to equal higher than 1.47Mpa (by Washburn equation-Washburn, the pressure that 1921-calculates for 1 micron pore size) and under being especially up to the mercury pressure (using above-mentioned machine) of 400MPa, be introduced into the cumulative volume of the mercury in hole, wherein this hole is assumed that cylindrical, assuming that mercury surface tension equals 480 dynes per centimeter and inorganic particle/mercury contact angle equals 140 °, volume of voids is with cm
3/ gram material provides.Volume of voids (the V of macropore
m) by measuring with following formula:
V
m=1/ρ
a-1/ρ
s-V
sm
ρ
athe apparent density (corresponding to its quality and the ratio of its volume) of product, 1/ ρ
afor the specific volume of this material, ρ
s(mainly) is the density of inorganic skeleton (product section occupied by densification/non-porous material), it is undertaken measuring by helium hydrometry, and (standard A STMC604-" compares the Standard Test Method of the true specific gravity for refractory materials of specific gravity hydrometer " by gas, ρ
sbe about 2000kg/m for silicon-dioxide
3this density therefore can divided by the factor of about 10 between the initial density and the density of final material of this particle, this alleviate especially by foamed and by for this purpose with the ratio of at least 65% volume introduce air (to obtain according to product of the present invention)) cause, 1/ ρ
sit is the specific volume of skeleton.
According to the total pore size volume (V of lagging material of the present invention
p=V
m+ V
sm) advantageously higher than 1.5cm
3/ g, and be preferably 5.5-18cm
3/ g.
According to lagging material of the present invention in the form of the solid foam (usual rigidity) for (or based on) porous silica silicon grain and, as has been described, obtained by the mixture of at least following key element especially: (above-mentioned) silica dioxide granule of water (or optional resistance aqueous foam), sub-micron pore porosity (is generally the dispersion/form of suspension of (in water), described particle has (initial, as being introduced in the particle in mixture) at least 5m
2(specific surface area is with m for the specific surface area S of/g
2/ g particle (one or more) provides), be greater than 50m especially
2/ g, if desired, (at least one) tensio-active agent and/or optional organic binder bond and/or mineral binder bond, and/or pore-creating agent, and/or fiber (or stiffener) etc., as explained hereinafter.
Therefore, more generally, the present invention relates to for heat insulation inorganic (mainly, as hereafter pointed out) foam (solid), this foam (being formed according to the said products of the present invention) is formed (this foam is named as " silicon dioxide foam ") by porous silica particle, and combine two different porosity ranges, there are 10 microns of first (greatly) aperture ranges to 3 mm dias, with have higher than 4nm and the second sub-micron porosity scope of diameter lower than 300nm, and its volume of voids is at least 1cm
3/ g, the density of this foam is lower than 300kg/m
3.
Having (greatly) hole, (this macroporosity derives from and spumes operation and correspond to the bubble introduced, the size of bubble and the substantially spherical macropore of generation are relative rules, there is more or less diameter Distribution that is narrow or compression, diameter Distribution especially between 50 microns to 500 microns, in structure (foam) as already mentioned), and the generation of the sub-micron pore porosity of this confinement air in region (or " wall ") between described (greatly) hole volume of voids of submicron level (or), improve the thermal characteristics of this product, obtain relatively lighter product (owing to there is these additional holes) simultaneously, this additional porosity in the wall of this foam is especially provided (exist in the particle used at first and usually produced by their synthesis) by intergranular pores porosity, and also produced by these porous particles stacking (to form the wall of foam).The foam so obtained according to the present invention has improved heat-insulating properties (relative to having the more traditional inorganic foamed of equal densities, or relative to common Porous-Organic shape polystyrene type insulation), and be that (more) is economical and keep light, and have than the better ageing resistance of the organic products with equal heat-proof quality and resistivity against fire simultaneously simultaneously.Described material/foam simultaneously with as packing material purposes and and surface applications, especially building surface purposes is compatible.
Be presented as lower than 40mW/m.K according to the thermal characteristics of insulation of the present invention, especially 20 to 40mW/m.K is approximately, be less than about 35mW/m.K greatly especially, and preferably approximately is lower than 30mW/m.K (in particular for via the insulation obtained according to the preferred method of the present invention), especially (entirety) thermal conductivity λ value (when thermal conductivity is low, this thermal characteristics is better) that 25mW/m.K is even lower is reduced to.Thermal conductivity λ (W/m.K) represents through this insulation (one meter of thickness, every m
2and when the temperature difference between two faces is 1 ° of K) the amount of heat.Use within the scope of this invention from Netzsch
tMthe value (at the same pressure and temperature, comparing under normal atmosphere (1 bar) and room temperature especially) of thermal conductivity λ measured by the HFM436 series under meter of company according to the working specification set up by standard A STMC518 and ISO8301.Characterizing temperature is about 25 DEG C, and under atmospheric pressure carry out this measurement, the Accuracy extimate of measurement is 5%.
As comparing, relative to similar but without obtain during porous particle and not there is the solid foam (having the inoganic solids foam of equal densities) of double porosity (and being only macropore), such as relative to (especially) by melting be then introduced into glass foam that glass in foaming furnace obtains (as below in comparative example illustrational those), the raising of the performance of heat conductivity aspect can be at least 20% or 25% (using according to method of the present invention), even at least 30% (reduction of thermal conductivity).
According to product of the present invention still than aerogel (its, due to their hydrophobicity, especially do not allow to obtain foam veritably and the double porosity do not produced as defined according to the present invention) more easily obtain, this aerogel is from precursor/starting material and obtain (and when according to product of the present invention to form inorganic substance (being formed their inorganic substance) by carrying out chemical reaction, what use (is therefore different from aerogel) – formed and carried out shaping and not the application target process (grinding etc.) that makes them degenerate or their chemical constitutions of object change process simply Wu machine Wu Zhi – inorganic particle, as as shown in method according to the present invention.Therefore advantageously do not use chemical reaction as mentioned previously or change according to the vesicular structure of product of the present invention and/or described product and formed.Can by compare exist in other field or application mesoporous-or nanometer-vesicular structure or foam (such as molecular sieve and such as obtained by precursor via sol-gel route those) carry out identical observation, this is mesoporous-or nano-porous structure or foam, there is different characteristics and restriction, usually operate generation by chemical reaction or by mechano-degradation.Product according to the present invention is more economical and simpler method acquisition via enforcement.
According to the apparent density of material of the present invention (or product or foam) lower than 300kg/m
3, this density can according to formula (additive, pH etc.) change and the condition that spumes (geometrical shape etc. of the time that spumes, stirring velocity, groove and blade).Density is measured by the ratio of the quality and described volume of setting up the given volume of material.Preferably, 200kg/m is less than or equal to according to the density of insulating material of the present invention
3, especially lower than 130kg/m
3, advantageously lower than 120kg/m
3, even lower than 100kg/m
3, even lower than 80kg/m
3.
Main (at least 80% weight of material according to the invention, even 90%) be, even only that mineral/inorganic (the optional organic materials existed can be organic binder bond if desired, organic grafting, etc.), this especially makes it possible to guarantee excellent resistivity against fire.This material also substantially (at least 80% weight, even 90%) is formed by the above-mentioned silica dioxide granule in foamy structure.These silica dioxide granules are solid and porous, and directly do not change their chemical formula for the formation of product.
This silica dioxide granule usually (at first) is powder type, its granularity is advantageously the median particle diameter D50 of 1 micron to 500 microns (especially 3-300 micron), this diameter is especially measured according to standard ISO 13320-1:2000 by using the sreen analysis of laser light scattering, if desired, make this powder dispersion, especially be dispersed in water and (especially can also add oil, such as surface-active effect and consolidation effect, and/or especially binding agent), and carry out using (or mixing) to be formed according to product of the present invention with the form of described dispersion.Preferably, particle size (D50) lower than 100 microns, especially lower than 10 microns.
The initial specific surface S of these silica dioxide granules is preferably higher than 30m
2/ g, especially higher than 50m
2/ g, especially higher than 100m
2/ g, this specific surface area is up to 500m especially
2/ g, and be especially advantageously 100-500m
2/ g even if desired, is 100-300m
2/ g (these particles usually and advantageously hydrophilic to be dispersed in water for when the component of this object or tensio-active agent not adding; This is because this specific surface area advantageously not more than above-mentioned maximum value to avoid the degeneration of the thermal characteristics caused due to described wetting ability).
This specific surface area, uses m
2/ g represents, is measured by nitrogen adsorption (the multiple gas adsorption theory by means of Brunauer, EmmettandTeller-BET method measures) according to standard ISO 9277:2010.
Preferably, the mineral substance forming this silica dioxide granule is soft silica, as precipitated silica, and Fumed silica, pyrolytic silicon dioxide, or silica gel.Precipitated silica and/or pyrolytic silicon dioxide (pyrolytic silicon dioxide as sold with trade mark HDK T30 by Wacker company) are particularly preferred.Particularly preferably, it is precipitated silica, such as, have 160m with trade mark Tixosil 365 by Rhodia Company
2the precipitated silica of/g specific surface area (being measured according to standard ISO 9277:2010 by BET).There is the diameter of 4nm to 200nm especially (namely granuloplastic by these according to the sub-micron porosity in product of the present invention, each hole of this kind has the diameter within the scope of this, the distribution of all diameters of these holes is more or less narrow or extruding), especially lower than 100nm.
If desired, the silica composition of several types (being such as combined fumed silica particle and precipitated silica particles to be formed according to product of the present invention) may also be made.
Except inorganic particle, material according to the invention also (is not got rid of by water or aqueous phase and also be there is another kind of medium, such as oil and/or alcohol, especially glycerol), medium formed, exist in the medium or mix inorganic particle, and making this medium spume (method according to what is called of the present invention " directly spumes ").Another kind method will be to use resistance aqueous foam (or the liquid of saponaceous outward appearance formed, random stacking acquisition by the gas foam in aqueous phase), particle is added (especially with dispersion in this resistance aqueous foam, it is normally moisture) (being called " mixing " method), but for preparation according to silicon dioxide foam of the present invention, it is preferred for directly spuming.This does not also have starting aqueous phase foamy (wherein particle before spuming) advantageously also to comprise at least one surface active cpd as previously noted.
Allow tensio-active agent especially aniorfic surfactant (salt) (positively charged ion or the nonionic surface active agent of excellent foamed, own for them, for during foamed, there is problem), be selected from following general formula compound especially: R-X
-, Y
+, wherein R is the aliphatic chain of 10-24 carbon atom, X
-the group (group such as carboxylate radical, sulfate radical, sulfonate radical) carrying negative charge, and Y
+it is the counter cation being selected from ammonium, sodium and potassium group, such as comprise the carboxylate salt of 12 to 24 carbon atoms, especially myristate, palmitate, stearate and oleate is selected from, or the conjugate base of mountain Yu's acid, such as, or the carboxylate salt produced from the process of tallow fatty acid, or other lipid acid conjugate base, comprise the shower soap/gel of the lipid acid from natural origin (as butter, Oleum Cocois etc.), such as tensio-active agent, as ammonium stearate etc.
But, because aniorfic surfactant be not absorbed in this silicon-dioxide surface on to promote the stabilization of this foam, preferably use at least one as the already mentioned zwitter-ion of tensio-active agent.In zwitter-ion, especially aminaocid or derivative etc. can be mentioned.According to the present invention, they are trimethyl-glycine preferably and advantageously, and as phosphorus trimethyl-glycine and/or ammonium trimethyl-glycine, and particularly preferably it is cocamidopropyl betaine (CAPB).Seem that CAPB is especially attracted on the surface of silicon-dioxide, guarantee certain electrostatic repulsion between particles simultaneously, so avoid their agglomeration, this interaction provides the extraordinary character and allow to obtain low density and relative little bubble size of spuming for particle, at this moment the silicon dioxide foam obtained is sufficiently stable (from draining and coalescent viewpoint), especially until its drying and between its dry epoch.
If desired, except at least one zwitter-ion, at least one second surface promoting agent (being also introduced in the mixture) or cosurfactant can also be used, this zwitter-ion at this moment main stability to this bubble works (time of this product drying), and cosurfactant can participate in such as on the other hand, as prevented Ostwald slaking.
Usually; this mixture (in order to prepare insulating material or granular mixture) comprises lower than 5%; advantageously lower than 2% one or more tensio-active agents, comprise the zwitter-ion that at least one is selected from trimethyl-glycine (ammonium trimethyl-glycine especially, preferred CAPB).This mixture is with lower than 2% especially, and the content of about 1% comprises at least one zwitter-ion especially, and lower than 1% other optional cosurfactant (one or more).
All right in the mixture, especially with the use of tensio-active agent in combination, use at least one pore-creating agent.Term in the present invention " pore-creating agent " represents any material that can produce porosity by means of the process being used for removing at least in part described reagent after embedding in this material by this reagent in material.If desired, allow additionally to improve volume of voids adding of pore-creating agent.The agglomerate of mineral substance becomes structurizing around pore-creating agent, removes the formation that described pore-creating agent causes porosity in a controlled manner.
Mineral substance is such as 0.2 to 3 relative to the weight ratio of pore-creating agent, especially 0.7 to 2.5.During this barrier product of preparation (especially after formation rigid foam), at least 10% (by weight) of pore-creating agent, especially at least 30%, especially at least 50%, preferably at least 90% be removed, such as, undertaken by calcining or washing.
Advantageously, pore-creating agent is formed by such material, and the calcining temperature of this material is lower than the fusing point of silicon-dioxide (this material is sealed in wherein) and/or sintering point.When precipitated silica, the calcining temperature of pore-creating agent such as should lower than 700 DEG C.
This pore-creating agent such as based on/be the particle form (it is normally spherical) of at least one organic materials (such as polymkeric substance), be especially colloidal form.It can be such as at least one organic granular, by comprise amphiphilic or stereoregular block (comprise block AB or ABA, wherein A represents hydrophilic block, as polyethylene oxide or polyacrylic acid and B represent that hydrophobic block is as polystyrene, poly(propylene oxide), polyisoprene or polyvinyl pyridine) (being total to) polymkeric substance composition.They can also be starch and/or NaCl type inorganic salt particle (be incorporated in aqueous mixture, this aqueous mixture comprises cosolvent if desired, and as ethanol, after this inorganic salt are removed by washing).Preferably, it is the colloidal dispersion of latex particle (one or more) and/or polymkeric substance (one or more) and/or the particle (one or more) that is made up of macromole (one or more), is selected from that one might rather say and produces spheroid those.This latex especially can comprise: vinyl type (being total to) polymkeric substance, advantageously vinylformic acid and/or carboxylic acid derivative type (being total to) polymkeric substance, the multipolymer (it does not carry out silanization) of vinylchlorid and alkene, etc.It can be the latex sold, as the urethane BaybondXP2602 by Bayer Company, the latex of oxidation or non-oxidized polyethylene wax form, optionally with acrylic copolymer (as sold by Rohm & Haas with from those of DowChemical company) together with, Styrene-acrylic copolymer or any acrylate copolymer (sold with Acronal series by BASF AG those) obtained by emulsion or dispersion radical polymerization, etc.Preferably, it is at least one water-dispersible acrylic copolymer (as sold by DSM N. V. with trade mark Neocryl those, as Neocryl XK-52, Neocryl BT21 or Neocryl BT100).The latex being used as pore-creating agent (one or more) advantageously has higher than 50 DEG C, especially 50-200 DEG C, the especially glass transition temperature Tg of 70-170 DEG C.
Pore-creating agent can use in emulsion or dispersion, and their mass content is such as the 5%-75% of the gross weight of this emulsion or dispersion, especially 20%-60%, even 30%-50%.
This mixture (for obtaining insulating material or granular mixture) can also comprise the organic and/or mineral binder bond of at least one, and it is such as allowing particle to be bonded to each other and/or for making particle be combined with the rest part of the structure of this material.
This binding agent can advantageously latex be (current, especially be selected from have formed film tendency those, this binding agent especially makes it possible to strengthen this foam), the aqueous emulsion of one or more natural or synthesized polymer materials or dispersion especially, it is normally thermoplastic.This latex adhesive preferably has lower than 50 DEG C,-50 DEG C to 25 DEG C especially, preferably-20 DEG C to 10 DEG C, the advantageously glass transition temperature Tg of-10 DEG C to 0 DEG C, and the film-forming temperature preferably had lower than room temperature, with obtain especially in field of house buildings for the intensity desired by the insulating material being applied to carrier.This latex can comprise vinyl type (being total to) polymkeric substance (such as based on vinyl acetate, polyvinyl acetate homopolymers especially, or based on the multipolymer of vinyl acetate and (methyl) vinylformic acid and/or ester, toxilic acid and/or ester, alkene and/or vinylchlorid, or based on vinylchlorid/ethylene copolymer), or acrylic-type (being total to) polymkeric substance (especially acrylonitrile/acrylate multipolymer, or vinylbenzene/silanization vinylformic acid or ester copolymer and/or carboxylic acid derivatives composition copolymer).This latex especially can be Styrene-acrylic copolymer or any acrylate copolymer.These latex be such as by BASF AG with title Acronal, especially Acronal S400 trade mark series sell those.
(usually at granular mixture or for obtaining in the mixture according to foam of the present invention/this product or in this foam) other additive can also be added, as rheological agent (softening agent, as glycerol, etc.), surface reagent, water-holding agent is (as gelatin or glycerol, etc.), opalizer (such as aluminium or the graphite of infrared light screening agent), mineral filler, or for strengthening other material (glass or the organic fibre of this physical strength, silicate, gypsum, cement, the organic binder bond of latex type as previously explained, etc.), or limit foam shrinks (glass microsphere etc.) or bubble is unbalanced and other material of their size (such as carrying out this foamed under perflexane atmosphere) of reduction, etc..
Especially, in order to prevent slaking, advantageously can add the cosurfactant of cationic surfactant or cationic polymers type, or Saponin/TSM, or the non-ionic polymers of ether of cellulose type (as Vltra tears), these different reagent can also have important effect during dried foam, shrink and/or (the ether of cellulose that breaks as reduced, as Vltra tears, reduce significantly especially and break).
Especially, can be prepared by least following key element according to lagging material of the present invention, described amount represents with the weight percent of the total mass relative to this mixture: the water of 40% to 95%, the silica dioxide granule of 5% to 60% and additive (one or more the) (binding agent of 0 to 15%, opalizer, hydrophobizing agent, tensio-active agent, pore-creating agent, etc.).
The present invention therefore make it possible to preparation the multiple height insulating material based on silicon-dioxide and, if desired, different additive, to cover large isolated range of application, especially in this buildings field.
This additive (especially tensio-active agent (one or more)) was usually introduced in granular mixture before introducing allows gas foamy; (mixed by particle in the second situation in established resistance aqueous foam, this foam can also use the solution that comprises described additive (comprising tensio-active agent (one or more)) or dispersion to be prepared before introducing the gas allowing foaming operation).
In the method according to the invention, the pH of this mixture can carry out regulating (when CAPB, being adjusted to about 8.5, because CAPB loses its some electric charges when peracidity pH), advantageously, especially before spuming in addition.
Forming step to be usually included in the cavity with suitable shape or cross section casting or molded comprise particle foam or the operation of spray foam on surface or wall.Term " is molded " should be understood and comprise any structural form in wide significance, extruding and extrudate chopping etc. as cast in open mould, through mould, dry usually after formation.
Can also comprise according to method of the present invention, if desired, after the drying, at least one allows to strengthen this material and/or if desired for removing the heat treatment step of pore-creating agent.
The method advantageously comprises the hydrophobization step (even if this material is hydrophobic) making the material of acquisition, this hydrophobization, under existing conditions, the thermal conductivity (such as not experiencing the product of this step, the highest by about 25%) reducing this foam is contributed to.
The lagging material obtained is solid (and normally rigidity) and multimode (especially bimodulus) porosity.It normally (is designed to) panel-form that its thickness at least equals 5mm.It can also obtain with the form of at least one layer (such as using on gypsum), although or still moistening material can be impregnated or be dispersed on net (such as non-woven fabric etc.), or this material can be combined etc. with fibre substrate or other layer.
This invention still further relates to according to the purposes of insulating material/foam of the present invention in building field, is particularly useful for the wall of isolated buildings.
The present invention and its advantage will more clearly be understood when reading the non-limiting example be as an example described below.
embodiment 1
In this embodiment, silicon dioxide foam is prepared as follows:
The precipitated silica sold with trade mark TixosilT365 by Rhodia company is made (to have about 3.5 microns of median particle diameter D50 and about 130m
2the specific surface area of/g) be dispersed in water, then the ammonium polyacrylate aniorfic surfactant sold with label Scha ü mungsmittelW53FL by Zschimmer & Schwartz company is added to this dispersion, water-holding agent (in the present embodiment: gelatin and glycerol, this glycerol also serves as softening agent) and mineral binder bond (here water glass), then use the mechanical stirring of stirrer to make the volume of the moistening foam so obtained approximate 3 times of the original volume of non-foamization dispersion.
Consisting of following (representing with weight percent) of this mixture: water: 73.4%; Precipitated silica: 18.2%; Water glass: 2.7%; Gelatin: 3.2%; Glycerol: 0.5%; Tensio-active agent: 1.9%.
Then this moistening silicon dioxide foam is made to cast in Teflon model and the temperature be placed on lower than 25 DEG C and in the baking oven of 80% relative humidity 3 days.Once dry, this foam or mashed prod, it has been subject to the mass loss of about 80%, hardens, in solid form.Then at 80 DEG C material all in one piece is placed on and comprises hexamethyldisilazane (HMDS) in the airtight chamber of hydrophobizing agent (this compound is sold with the label 52619 of Fluka trade mark by Sigma – Aldrich company) 4 hours.
Have according to two porosity ranges of the present invention (there are 10 microns of macropores to 3mm diameter especially and have higher than 4nm and lower than the sub-micron porosity of the diameter of 300nm) and the product comprising the acquisition of the air being greater than 65% volume then characterize according to the method mentioned hereinbefore, the value of acquisition is as follows:
-density: 200kg/m
3;
-there are 10 microns of volume of voids to the macropore of 3mm diameter: at least 3.3cm
3/ g;
-there is the volume of voids of the sub-micron porosity of 4nm to 300nm diameter: 1.25cm
3/ g;
-heat conductivity: 36mW/m.K.
The Accuracy extimate measured is 5%.
The heat insulation inorganic materials that the value display pointed out obtains has the important porosity that low density has two type porositys (comprising the hole of the diameter with 4nm to 300nm) simultaneously, and has particularly advantageous thermal characteristics.
Embodiment 2
In water, precipitated silica (as in embodiment 1, by Rhodia company with trade mark TixosilT365 product sold) is made water in carry out pre-dispersed with 25% weight by ul-trasonic irradiation (using ultrasonic probe or bath).Making pH regulator to 8.5 by adding sodium hydroxide, then adding water to reach the last silica concentration of 22% and again to make this dispersion homogeneous by ul-trasonic irradiation.
Then add ether of cellulose (with trade mark Methocel311 by DowChemicalCompany Company) with the ultimate density of 0.25%, when it can be reduced in drying, this silicon dioxide foam breaks.Make this dispersion homogenizing several minutes again by ul-trasonic irradiation, the mixture of acquisition is uniform.
Then with 0.3 milligram/m
2the concentration (i.e. 0.045 gram of/gram of silicon-dioxide) of silicon-dioxide specific surface area adds amphoteric ionic surfactant CAPB (by Goldschmidt Company).This mixture becoming more viscosity carries out homogenizing by supersound process again, then uses the drum agitation mixing machine (robotmixeurrotatif) of trade mark ElekomEK719 to carry out spuming of this silica dispersion.
Then moistening foam is dispensed on multiple Teflon and evaporates in crucible, then in the climatic chamber of 35 DEG C and 80% relative humidity, carries out drying.Then in Teflon reactor, this silicon dioxide foam was made to carry out hydrophobization process 4 hours periods by the reaction of the hexamethyldisilazane (HMDS) (sample is positioned in the confined chamber comprising liquid HMDS, and liquid HMDS evaporates and is absorbed in the surface of material) with vapor phase at 80 DEG C.Once this process completes, make this reactor cooling to room temperature before opening, the sample of the solid foam of acquisition then carry out processing especially make their face be plane with parallel, during a weekend, sample also carries out stabilization in ambient atmosphere.
Have according to two porosity ranges of the present invention (have 10 microns of macropores to 3 mm dias especially and have higher than 4nm and lower than the sub-micron porosity of the diameter of 300nm) and comprise then characterizing according to the method mentioned hereinbefore before and after hydrophobization according to product of the present invention of the acquisition of the air being greater than 65% volume, the value of acquisition is as follows:
-density: 130kg/m
3;
-specific surface area: 150m
2/ g;
-there are 10 microns of volume of voids to the macropore of 3 mm dias: at least 6cm
3/ g;
-there is the volume of voids of the sub-micron porosity of 4nm to 300nm diameter: 1.3cm
3/ g;
-thermal conductivity before hydrophobization: 35mW/m.K;
-thermal conductivity after hydrophobization: 29mW/m.K.
Observe, by means of according to the preferred method of the present invention obtain material, especially by means of using Cocamidopropyl as tensio-active agent, there is the thermal conductivity relative to being further improved by means of the material especially using the general method of aniorfic surfactant (as ammonium stearate) to obtain.And hydrophobization reduces the thermal conductivity of foam further.
The stability of the silicon dioxide foam using tensio-active agent CAPB to obtain is also compared with the stability (and they produce the ability of silicon dioxide foam) of other silicon dioxide foam using other tensio-active agent to obtain.
For this reason, often kind of suspension by disperseing this precipitated silica (with trade mark TixosilT365 by Rhodia Company) to be prepared in distilled water.By means of sodium hydroxide solution (2M) by pH regulator to 8.5, in ultrasonic bath, then stir this suspension 5 hours.Then be added in suspension by tensio-active agent, the silica concentration in this suspension is 15.9% weight and surfactant concentration is 0.5%.
Then 5.5 grams of suspension to be positioned in 30 milliliters of cylindrical glass containers and to measure the volume Vs of this suspension.Then, rotary mixer is used to stir this suspension 1 minute.Measure the volume Vm of the foam of this formation (if there is no formation of foam, Vm=Vs), the volume fraction of mixing at first in this foam is defined as ratio F0=(Vm-Vs)/Vm, and this volume fraction allows the frothiness (forming the ability of foam) evaluating this suspension.Then make container one hour at room temperature and atmospheric pressure, again measure the volume of foam, evaluate the volume fraction (F1) of the air still existed, the Evaluation accuracy of the measurement of F0 and F1 is 5%.
Use the amphoteric ionic surfactant CAPB of the present embodiment, the value of F0 and F1 of acquisition is each is 60%.
Use cationic surfactant as the palmityl trimethyl ammonium chloride (CTAC) by Sigma Company, silicon dioxide foam (F0=F1=0%) can not be obtained, similarly, use by the amphoteric ionic surfactant of Cocamidopropyl hydroxyl sulfo betaine (CHS) type (being different from trimethyl-glycine) of Rhodia Company also like this.
Use aniorfic surfactant as the Zetesol NL (SLES) by Stepan Company, easily obtain silicon dioxide foam (F0=60%), but it sufficiently can not be saved (F1=0%) along with the time.
Therefore the use of tensio-active agent CAPB is particularly advantageous relative to other tensio-active agent, especially allows to obtain along with time sufficiently stable foam is to allow its drying and its solidification.
comparative example
In this embodiment, measure with the characteristic of label FoamGlasS3 by the glass foam of FoamglasBuilding Company.This foam is purely inorganic and has the density with the identical magnitude of density of product according to the present invention.But different from product according to the present invention, it only has a porosity ranges (having the macropore higher than the diameter of 10 microns).The value obtained is as follows:
-density: 130kg/m
3;
-there is the volume of voids of the macropore higher than 10 micron diameters: 7.2cm
3/ g;
-heat conductivity: 45mW/m.K.
The Accuracy extimate measured is 5%.
Observe, in equal density, according to the heat-insulating properties of product of the present invention more much better than the heat-insulating properties of " single mode hole " foam in the present embodiment (as comparing object, referring to according to embodiments of the invention 2).
Product according to the present invention is that to be particularly suitable for high-performance heat insulation, especially in the building field for isolated building walls (exterior wall or interior wall).According to product of the present invention, also there is sound dampening properties or the application that sound insulation neutralization has lightening material can be used advantageously in.
Claims (13)
1. lagging material, it is formed by the silica dioxide granule with sub-micron pore porosity, this material has two different porosity ranges, comprise the first scope be made up of the macropore of the diameter with 10 microns to 3 millimeters, with by having higher than 4nm and the second scope formed lower than the sub-micron porosity of the diameter of 300nm, the volume of voids of described sub-micron porosity is at least 1cm
3the density of/g and described lagging material is lower than 300kg/m
3.
2. lagging material according to claim 1, is characterised in that it is solid foam form.
3. lagging material according to claim 1, is characterised in that it is mainly inorganic.
4. according to the lagging material of any one of claim 1-3, be characterised in that it is obtained by the mixture of at least following key element: water or resistance aqueous foam, the silica dioxide granule of sub-micron pore porosity, this particle is incorporated in this foam or water with the form of dispersion/suspension usually, and described particle has higher than 5m
2the specific surface area S of/g.
5., according to the lagging material of any one of claim 1-3, be characterised in that this silica dioxide granule is based on soft silica.
6., according to the lagging material of any one of claim 1-3, be characterised in that the volume of voids of this sub-micron porosity is 1-3cm
3/ g, the volume of voids of macropore is higher than 1cm
3/ g.
7., according to the lagging material of any one of claim 1-3, be characterised in that it has the thermal conductivity lower than 40mW/m.K.
8. the heat insulation purposes of buildings is used for according to the material of any one of claim 1-7.
9., according to the preparation method of the lagging material of any one of claim 1-7, comprise the following steps:
-at least one preparation has higher than 5m
2the specific surface area S of/g, and in the porosity ranges of 4nm to 300nm, there is at least 1cm
3the step of the silica dioxide granule mixture of the volume of voids of/g;
-at least one preparation comprises the step of the foam of described particle;
-at least one forming step;
-at least one at least part of dry so foam of acquisition or step of material.
10. method according to claim 9, is characterised in that in granular mixture or adds at least one additive in the foam, and it is selected from pore-creating agent, tensio-active agent, organic or mineral binder bond, rheological agent, surface reagent and/or stiffener.
11. for the preparation of the method for the lagging material based on silicon-dioxide, wherein this lagging material has two different porosity ranges, comprise the first scope be made up of the macropore of the diameter with 10 microns to 3 millimeters, with by having higher than 4nm and lower than the second scope that the sub-micron porosity of the diameter of 300nm forms, comprising the following steps:
-at least one preparation has higher than 5m
2the specific surface area S of/g, and there is in 4-300nm porosity ranges at least 1cm
3the step of the mixture of the silica dioxide granule of the volume of voids of/g;
-at least one to be prepared the step of foam by described granular mixture by mixing at least one zwitter-ion, and this zwitter-ion is selected from trimethyl-glycine;
-at least one forming step;
-at least one at least part of dry so foam of acquisition or step of material.
12. methods according to claim 11, are characterised in that it is the method preparing silicon dioxide foam.
13., according to the method for claim 11 or 12, are characterised in that it also comprises at least one hydrophobization step.
Applications Claiming Priority (3)
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|---|---|---|---|
| FR1156429A FR2977888B1 (en) | 2011-07-13 | 2011-07-13 | THERMAL INSULATION MATERIALS HIGH PERFORMANCE. |
| FR1156429 | 2011-07-13 | ||
| PCT/FR2012/051666 WO2013007958A1 (en) | 2011-07-13 | 2012-07-12 | High-performance thermal insulation materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103781830A CN103781830A (en) | 2014-05-07 |
| CN103781830B true CN103781830B (en) | 2016-04-27 |
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|---|---|---|---|
| CN201280044527.3A Expired - Fee Related CN103781830B (en) | 2011-07-13 | 2012-07-12 | High performance lagging material |
Country Status (6)
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| EP (1) | EP2731986B1 (en) |
| JP (1) | JP6228115B2 (en) |
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| FR2969186B1 (en) * | 2010-12-15 | 2014-01-10 | Saint Gobain Rech | PROCESS FOR PREPARING INSULATING MATERIAL |
| KR102524875B1 (en) | 2015-05-19 | 2023-04-25 | 바스프 에스이 | Articles containing tubular particles |
| DE102015216505A1 (en) * | 2015-08-28 | 2017-03-02 | Wacker Chemie Ag | Silica moldings with low thermal conductivity |
| KR102543511B1 (en) * | 2018-07-17 | 2023-06-15 | 에보니크 오퍼레이션즈 게엠베하 | Thermal insulation composition based on fumed silica granules and process for its preparation |
| CN110204210B (en) * | 2019-05-27 | 2021-10-08 | 蚌埠学院 | Glass wool thermal insulation material, preparation process and application |
| WO2022180087A1 (en) * | 2021-02-25 | 2022-09-01 | Hipor Materials Ab | Insulation material and method for production thereof |
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| CN1668372A (en) * | 2002-05-15 | 2005-09-14 | 卡伯特公司 | Aerogel and hollow particle binder composition, insulation composite, and method for preparing the same |
| WO2010129200A1 (en) * | 2009-04-27 | 2010-11-11 | Ulrich Bauer | Aerogel compositions and methods of making and using them |
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| EP0184926B1 (en) * | 1984-12-08 | 1989-03-01 | Micropore International Limited | Panels of microporous thermal insulation |
| US5549990A (en) * | 1986-03-24 | 1996-08-27 | Ensci Inc | Battery element containing porous particles |
| EP0647603A1 (en) * | 1993-10-11 | 1995-04-12 | Hans Beat Fehlmann | Building element with improved strength |
| US5786294A (en) * | 1996-05-10 | 1998-07-28 | Northwestern University | Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure |
| CN1227157C (en) * | 2001-09-25 | 2005-11-16 | 三菱化学株式会社 | Silica |
| WO2005023918A1 (en) * | 2003-08-27 | 2005-03-17 | Idemitsu Kosan Co., Ltd. | Thermoplastic resin composition for foamed product and foamed product therefrom |
| JP2004010423A (en) * | 2002-06-06 | 2004-01-15 | Matsushita Electric Ind Co Ltd | Solid heat insulating material and its manufacturing method |
| WO2006134080A1 (en) * | 2005-06-15 | 2006-12-21 | Solvay (Société Anonyme) | Use of particles of calcium carbonate in the production of construction materials |
| KR100709075B1 (en) * | 2006-05-08 | 2007-04-18 | 주식회사 마스타테크론 | Method for preparing mesoporous silica and the mesoporous silica therefrom |
| EP1892226A3 (en) * | 2006-08-25 | 2010-02-17 | H+H Deutschland GmbH | Process for reducing the heat conductivity of calcium silicate building blocks and calcium silicate building blocks with improved heat conductivity |
| TW200835648A (en) * | 2007-02-26 | 2008-09-01 | Ind Tech Res Inst | Porous material and method for preparing the same |
| JP2010047710A (en) * | 2008-08-22 | 2010-03-04 | National Institute Of Advanced Industrial Science & Technology | Foamed polymer-silica composite having flexibility and moldability, and heat insulation material using the same |
| FR2948884B1 (en) * | 2009-08-05 | 2012-06-01 | Air Liquide | POROUS CERAMIC MATERIAL HAVING POROGENIC STACK CONTROLLED MACROPOROSITY |
| US9102076B2 (en) * | 2009-11-25 | 2015-08-11 | Cabot Corporation | Methods for making aerogel composites |
| FR2955863B1 (en) * | 2010-02-03 | 2012-03-09 | Saint Gobain Rech | HIGH PERFORMANCE THERMAL INSULATION MATERIALS |
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| FR2977889B1 (en) * | 2011-07-13 | 2014-01-10 | Saint Gobain Isover | HIGH PERFORMANCE THERMAL INSULATION MATERIALS |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1668372A (en) * | 2002-05-15 | 2005-09-14 | 卡伯特公司 | Aerogel and hollow particle binder composition, insulation composite, and method for preparing the same |
| WO2010129200A1 (en) * | 2009-04-27 | 2010-11-11 | Ulrich Bauer | Aerogel compositions and methods of making and using them |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013007958A1 (en) | 2013-01-17 |
| US20140166248A1 (en) | 2014-06-19 |
| EP2731986B1 (en) | 2020-02-12 |
| CN103781830A (en) | 2014-05-07 |
| US10119775B2 (en) | 2018-11-06 |
| FR2977888A1 (en) | 2013-01-18 |
| EP2731986A1 (en) | 2014-05-21 |
| FR2977888B1 (en) | 2014-01-10 |
| JP2014526002A (en) | 2014-10-02 |
| JP6228115B2 (en) | 2017-11-08 |
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